Reaction product of certain acid and alkanolamine

ABSTRACT

Reaction product formed by the condensation of certain alkanolamines with polyhalopolyhydropolycyclicdicarboxylic acids of the formula hereinafter given, its corresponding anhydride, corresponding diol or ester. These compounds have utility as stabilizers against deterioration of organic substances, such as lubricants, hydrocarbon oils and plastics, as well as possessing insecticidal properties.

United States Patent Inventor Appl. No.

Henryk A; Cyba Evanston, Ill.

Apr. 10, 1968 Dec. 7, 1971 Universal Oil Products Company Des Plaines,Ill.

Continuation-impart of application Ser. No. 329,979, Dec. 12, 1963, nowabandoned. This application Apr. I0, 1968, Ser. No. 720,339

REACTION PRODUCT OF CERTAIN ACID AND ALKANOLAMINE 17 Claims, No DrawingsU.S. Cl

R, 260/75 N, 260/78 TF, 260/78 UA, 260/485 G, I

260/485 H, 260/5 [4 B, 260/557 B, 260/6l7 F Primary Examiner-Lewis GottsAssistant ExaminerRobert Gerstl Attorneys-James R. Hoatson, Jr. andBernard L. Kramer ABSTRACT: Reaction product formed by the condensationof certain alkanolamines with polyhalopolyhydropolycyclicdicarboxylicacids of the formula hereinafter given, its corresponding anhydride,corresponding diol or ester. These compounds have utility as stabilizersagainst deterioration of organic substances, such as lubricants,hydrocarbon oils and plastics, as well as possessing insecticidalproperties.

REACTION PRODUCT OF CERTAIN ACID AND ALKANOLAMINE CROSS-REFERENCE TORELATED APPLICATIONS This is a continuation-in-part of copendingapplication Ser. No. 329,979, filed Dec. 12, 1963, now abandoned.

DESCRlPTION OF THE INVENTION This application relates to a novelcomposition of matter comprising the reaction product of a particulartype of dicarboxylic acid or derivative thereof with an alkanolamine.

In one embodiment, the present invention relates to the reaction productof a compound selected from the group consisting ofpolyhalopolyhydropolycyclicdicarboxylic acid and derivative thereof withan alkanolamine.

In another embodiment, the present invention relates to the use of thereaction product as an additive in organic substances includinghydrocarbon oils and particularly lubricants, as well as plastics,textiles, etc., requiring flame-proofing properties.

As hereinbefore set forth, the reaction product of the present inventionis prepared by the reaction of a particular dicarboxylic acid orderivative thereof with an alkanolamine. The particular type of acid foruse in the present invention is apolyhalopolyhydropolycyclicdicarboxylic acid and, in a preferredembodiment, comprises the acid or the anhydride thereof. Any suitableacid or anhydride meeting these requirements is used in accordance withthe present invention. In one embodiment the acid or anhydride is of thetype known in the art as Chlorendic or I-IET" acid or anhydride. Thisacid is prepared by the Diels-Alder addition reaction of maleic acid andhexachorocyclopentadiene or more conveniently by the reaction of maleicanhydride and hexachlorocyclopentadiene to form the correspondinganhydride and then hydrolyzed to form the acid. The correspondinganhydride is prepared by the reaction of maleic anhydride andhexachlorocyclopentadiene. This acid or anhydride also may be namedl,4,5,6,7,7-hexachlorodicyclo-(2.2. l )-5-heptene-2,3-dicarboxylic acidor the corresponding anhydride. These compounds are prepared by thereaction of equal molar quantities of the reactants, generally byrefluxing preferably at about 350 F. in the presence of a solvent. Thesereactions are well known in the art and are described, for example, inUS. Pat. No. 2,606,910 and elsewhere.

In place of maleic acid or maleic anhydride, it is understood that othersuitable dicarboxylic acids containing carbon to carbon unsaturation maybe employed. Illustrative examples include fumaric acid, itaconic acid,citraconic acid, glutaconic acid, etc. Also, in place ofhexachlorocyclopentadiene, other suitable halo-substitutedcycloalkadienes may be used. Illustrative examples includel,Z-dichlorocyclopentadiene, 1,5- dichlorocyclopentadiene,l,2,3-trichlorocyclopentadiene, l,2,3,4-tetrachlorocyclopentadiene,1,2,3 ,4,S-pentachlorocyclopentadiene and similar compounds in which allor part of the chlorine is replaced by other halogen and particularlybromine.

A particularly preferred polyhalopolyhydropolycyclicdicarboxylic acid oranhydride is prepared by the Diels-Alder condensation of a conjugatedaliphatic diene with an olefinic dicarboxylic acid and then furthercondensing the resultant cyclohexenedicarboxylic acid with ahalocycloalkadiene. A specifically preferred reaction product is theDiels-Alder condensation of l,3-butadiene with maleic anhydride to forml,2,3,6-tetrahydrophthalic anhydride, followed by the Diels- Aldercondensation with hexachlorocyclopentadiene. The product may be named5,6,7,8,9,9-hexachloro- 1,2,3,4,4a,5 ,8,Ba-octahydro-S,8-methano-2,3-naphthalenedicarboxylic anhydride, hereinafter referred to as "A"anhydride. The corresponding acid is prepared preferably by startingwith maleic anhydride as above and hydrolyzing the formed A" anydride tothe A acid. The acid may be named 5,6,7,8,9,9-hexachloro-l,2,3,4,4a,5,8,8aoctahydro-5,8-methano-2,3-naphthalene-dicarboxylic acid,hereinafter referred to as A acid. Here again, other conjugatedaliphatic dienes may be used including, for example, 2- methyll,3-butadiene, 1,3-pentadiene, l,3hexadiene, 2,4hexadiene,2,3-dimethyl-l,3butadiene, 1,3-heptadiene, 2,4-heptadiene, conjugatednonadienes, etc., halodienes as, for example, chloroprene andparticularly l-chlorobutadiene and 1,4- dichlorobutadiene. Similarly,other unsaturated dicarboxylic acids may be used including fumaric acid,itaconic acid, citraconic acid, glutaconic acid, mesaconic acid, etc.Also, other halocycloalkadienes may be used including, for example,those specifically hereinbefore set forth. The preparation of thesecompounds also is known in the art and is set forth in detail in 0.8.Pat. No. 3,017,431. 3

Still another preferred polyhalopolyhydropolycyclicdicarboxylic acid oranydride is prepared by condensing cyclopentadiene with maleic acid ormaleic anhydride to form norborn- 5-ene-2,3-dicarboxylic acid oranhydride and then condensing the same with hexachlorocyclopentadiene.The product may be named 5,6,7,8,9,9-hexachloro-l,2,3,4,4a5,8,8a-octahydrol,4,5,8,-dimethano-2,3-naphthalenedicarboxylicacid or anhydride, hereinafter referred to as 3" acid and 8" anhydriderespectively. I-Iere again, it is understood that other conjugatedcycloaliphatic dienes, other unsaturated dicarboxylic acids oranhydrides and other polyhalocycloalkadienes may be used to preparesuitable polyhalopolyhydropolycyclicdicarboxylic acids or anhydrides.

From the above, it will be seen that any suitablepolyhalopolyhydropolycyclicdicarboxylic acid or anhydride trated by thefollowing general structure:

in which X is sele ted from the group consisting of halogen andparticularly chlorine and/or bromine, hydrogen and an alkyl radical offrom one to 10 and preferably from one to four carbon atoms, at leasttwo of the Xs being halogen, Y is selected from the group consisting ofhalogen, hydrogen and an alkyl radical of one to 10 and preferably fromone to four carbon atoms, m is an integer of from one to four, n rangesfrom zero to four and p ranges from zero to four.

The above structure illustrates the dicarboxylic acid. In the interestof simplicity, the corresponding anhydride is not being illustrated, butis readily ascertainable from the above structure.

Referring to the above structure, when X is chlorine, m is one, n iszero and p is zero, the compound is l,4,5,6,7,7-hexachlorobicyclo-(2.2.l)-5-heptene-2,3-dicarboxylic acid or the corresponding anhydride.Similarly, when X is chlorine, m is one, n is zero and p is one, thecompound is 5,6,7,8,9,9-hexachlorol ,2,3 ,4,4a,5 ,8 ,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylic acid or the correspondinganhydride. Also, when X is chlorine, Y is hydrogen, m is one, n is oneand is one, the compound is 5,6,7,8,9,9hexachlrol,2,3,4,4a,5,8,8a-octahydro-l ,4,5,8-dimethano-2,3-

napththalenedicarboxylic acid or the corresponding anhydride.

While the particular acid or anhydride set forth above is preferred, itis understood that an ester of the acid may be used for reacting withthe alkanolamine. Any suitable ester may be used and is prepared byreacting the acid or anhydride with an alcohol under conditions toliberate water. While the alcohol may contain from one to 18 carbonatoms, it preferably contains one to four carbon atoms. Illustrativealcohols include methanol, ethanol, propanol, butanol, pentanol,hexanol, etc.

In still another embodiment the corresponding mono or diol of thedicarboxylic acids set forth above may be used. The diol is readilyprepared by reacting hexachlorocyclopentadiene with l,4-butenediol in amanner similar to that described previously to form the diolcorresponding to Chlorendic acid. In another example, the diol isprepared by reacting hexachlorocyclopentadiene with alpha-allyl glycerolether. These reactions are well known in the art and are described forexample, in U.S. Pat. No. 3,007,958. Similarly,hexachlorocyclopentadiene is reacted with 2,3-dimethanolcyclohex-5- eneto form the diol corresponding to the A acid. It is understood that anysuitable mono or diol of the dicarboxylic acid set forth above may beused for reacting with the alkanolamine. In another embodiment the diolis reacted with a dicarboxylic acid or anhydride, either prior to orsimultaneously with the reaction with the alkanolamine. Illustrativedicarboxylic acids include malonic acid, succinic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,etc., and the corresponding anhydrides. The reaction is readily effectedby refluxing the mixture, preferably in the presence of a solventincluding aromatic hydrocarbons as benzene, toluene, xylene, cumene,etc., or other solvents such as decalin.

As hereinbefore set forth, the dicarboxylic acid, anhydride, esterand/or diol is reacted with an alkanolamine. In one embodiment thealkanolamine comprises a monoalkanolamine, preferably containing fromtwo to twenty carbon atoms, including ethanolamine, propanolamine,butanolamine, pentanolamine, hexanolamine, heptanolamine, octanolamine,

nonanolamine, decanolamine, undecanolamine, dodecanolamine,tridecanolamine, tetradecanolamine, pentadecanolamine, hexadecanolamine,heptadecanolamine,

ocatadecanolarnine, nonadecanolamine, eicosanolamine, etc., andparticularly these alkanolamines in which one or or both of the aminohydrogens is replaced by an alkyl group, the alkyl group containing fromone to 50 and preferably from one to 20 carbon atoms. Illustrativesubstituted alkanolamines include N-methyl-ethanolamine,N-ethyl-ethanolamine, N- propyl-ethanolamine, N-butyl-ethanolamine,N-pentylethanolamine, N-hexyl-ethanolamine, N-heptylethanolamine,N-octyl-ethanolamine, N-nonyl-ethanolamine, N-decyl-ethanolamine,N-undercyl-ethanolamine, N-dodecylethanolamine, N-tridecyl-ethanolamine,N-tetradecylethanolamine, N-pentadecyl-ethanolamine,N-hexadecylethanolamine, N-heptadecyl-ethanolamine,N-octadecylethanolamine, N-nonadecyl-ethanolamine,N-eicosylethanolamine, etc., N,N-dimethyl-ethanolamine,N,N-diethylethanolamine, N,N-dipropyl-ethanolamine,N,N-dibutylethanolamine, N,N-dipentyl-ethanolamine,N,N-dihexylethanolamine, N,N-diheptyl-ethanolamine,N,N-dioctylethanolamine, N,N-dinonyLethanolamine,N,N-didecylethanolamine, N,N-diundecyl-ethanolamine,N,N-didodecylethanolamine, N,N-ditridecyl-ethanolamine, N,N-ditetradecyl-ethanolamine, N,N-dipentadecyl-ethanolamine,N,N-dihexadecyl-ethanolamine, N,N-diheptadecylethanolamine,N,N-dioctadecyl-ethanolamine, N,N- dinonadecyl-ethanolamine,N,N-dieicoxyl-ethanolamine, etc., as well as similarly substitutedalkanolamines in which the alkanol moiety contains from three to 20carbon atoms. It is un derstood that the alkanolamine may contain analiphatic substituent attached to one or more of the carbon atomsforming the alkanol group. Furthermore, it is understood that a mixtureof the alkanolamines may be used, preferably being selected from thosehereinbefore set forth, and also that the substitution may comprisecycloalkyl and particularly cyclohexyl.

In another and preferred embodiment, the alkanolamine contains at leasttwo hydroxyl groups and one amino group or at least one hydroxyl groupand two amino groups. The use of such alkanolamines results in a polymerformation. The embodiment of the alkanolamine containing two hydroxyland one amino groups are dialkanolamines and preferably N-aliphatic-dialkanolamines in which the aliphatic group attached to thenitrogen atom contains from one to about 50 carbon atoms and preferablyfrom about eight to about 22 carbon atoms. In a particularly preferredembodiment, the aliphatic group contains from one to about 20 carbonatoms each. The alknnol groups preferably contain from about two toabout four carbon atoms each, although it is understood that they maycontain up to about 20 carbon atoms each. Preferably theN-aliphatic-dialkanolamine is an N-alkyldiethanolamine. Illustrativecompounds include N-methyldiethanolamine, N-ethyl-diethanolamine,N-propyldiethanolamine, N-butyl-diethanolamine, N-pentyldiethanolamine,N-hexyl-diethanolamine, N-heptyldiethanolamine, Noctyl-diethanolamin,N-nonyldiethanolamine, N-decyl-diethanolamine, N-undecyldiethanolamine,N-dodecyl-diethanolamine, N-triclecyldiethanolamine,N-heptatriacontyl-diethanolamine, N-octatriacontyl-diethanolamine,N-nonatriacontyldiethanolamine, N-tetracontyl-diethanolamine,N-hentetracontyl-diethanolamine, N-dotetracontyl-diethanolamine,N-tritetracontyl-diethanolamine, N-tetratetracontyldiethanolamine,N-pentatetracontyl-diethanolamine, N-hexatetracontyl-diethanolamine,N-heptatetracontyldiethanolamine, N-octatetracontyl-diethanolamine, N-nonatetracontyl-diethanolamine, N-pentacontyldiethanolamine, etc. Insome cases, N-alkenyldiethanolamines may be utilized. IllustrativeN-alkenyldiethanolamines include N-hexenyl-diethanolamine,N-heptenyl-diethanolamine, N-octeny-diethanolamine,N-noneyldiethanolamine, N-decenyl-diethanolamine,N-undecenyldiethanolamine, N-dodecenyl-dietanolamine,N-tridecenyldiethanolamine, N-tetradecenyl-diethanolamine,N-pentadcenyl-diethanolamine, N-hexadecenyl-diethanolamine,N-heptadecenyl-diethanolamine, N-octadecenyl-diethanolamine, N-nonadecenyl'diethanolamine, N-eicosenyl-diethanolamine, etc.

It is understood that the N-aliphatic-diethanolamines may contain analiphatic substituent attached to one or both of the carbon atomsforming the ethanol groups. These compounds may be illustrated byN-aliphatic-di-( l-methyl-ethanolamine), N-aliphatic-di-(lethyl-ethanolamine), N-aliphatic-di-( lpropyl-ethanolamine),N-aliphatic-di-( l-butyl-ethanolamine N-aliphatic-di-(l-pentyl-ethanolamine), N-aliphatic-di-( lhexyl-ethanolamine), etc.,N-aliphatic-di-(Z-methylethanolamine),N-aliphatic-di-(2N-aliphatic-di-(2-propylethanolamine),N-aliphatic-di-(Z-butyl-ethanolamine), N-aliphatic-di-(Z-pentyI-ethanolamine),N-aliphatic-di-(Z-hexylethanolamine etc. It is understood that thesespecific compounds are illustrative only and that other suitablecompounds containing diethanolamine configuration may be employed.

The specific compounds hereinbefore set forth are examples ofN-aliphatic-diethanolamines. Other N-aliphatic-dialkanolamines includeN-aliphatic-dipropanolamines and N- aliphatic-dibutanolamines, althoughN-aliphatic-dipentanolamines, N-aliphatic-dihexanolamines and higherdialkanolamines may be used in some cases. It is understood that thesedialkanolamines may be substituted in a manner similar to thatspecifically described hereinbefore in connection with the discussion ofthe diethanolamines. Furthermore, it is understood that mixtures ofN-aliphatic-dialkanolamines may be employed, preferably being selectedfrom those hereinbefore set forth, and also that the substitution maycomprise cycloalltyl and particularly cyclohexyl. Also, it is understoodthat the various dialkanolamines are not necessarily equivalent.

A number of N-alkyl-diethanolamines are available commercially and areadvantageously used in preparing the condensation product. For example,N-tallow-diethanolamine is available under the trade name of Ethomeen T/12. This material is a gel at room temperature, has an average molecularweight of 354 and a specific gravity at 25/25 C. of 0.916. The alkylsubstituents contain from about 12 to carbon atoms per group and mostly16 to 18 carbon atoms. Another mixed product is available commerciallyunder the trade name of Ethomeen 8/12 and is N-soya-diethanolamine. Itis a gel at room temperature, has an average molecular weight of 367 anda specific gravity at l25 C. of 0.911. The alkyl substituents contain 16to 18 carbon atoms per group. Still another commercial product isEthomeen C/12, which is N-coco-diethanolemine,, and is a liquid at roomtemperature, and has an average molecular weight of 303 and a specificgravity at 25l25 C. of 0.874. The alkyl groups contain mostly 12 carbonatoms per group, although it also contains groups having from eight to16 carbon atoms per group. Still another commercially available productis N-stearyl-diethanolamine, which is marketed under the trade name ofEthomeen 18/ 12. This product is a solid at room temperature, has anaverage molecular weight of 372 and a specific gravity at 25/25 C. of0.959. It contains 18 carbon atoms in the alkyl substituent.

When the alkanolamine contains one hydroxyl and two amino groups, apreferred alkanolamine is aminoalkyl alkanolamine. The alkanolaminepreferably contains from four and preferably from six to about 50 carbonatoms. Illustrative compounds include aminoethyl ethanolamine,aminoethyl propanolamine, aminoethyl butanolamine, aminoethylpentanolamine, aminoethyl hexanolamine, etc., aminopropyl ethanolamine,aminopropyl propanolamine, aminopropyl butanolamine, aminopropylpentanolamine, aminopropyl hexanolamines etc., aminobutyl ethanolamine,aminobutyl propanolamine, aminobutyl butanolamine, aminobutylpentanolamine, aminobutyl hexanolamine, etc., aminopentyl ethanolamine,aminopentyl propanolamine, aminopentyl butanolamine, aminopentylpentanolamine, aminopentyl hexanolamine, etc., aminopentyl ethanolamine,aminohexyl propanolamine, aminohexyl butanolamine, aminohexylpentanolamine, aminohexyl hexanolamine, etc. Here again, one or both ofthe nitrogen atoms of the aminoalkyl alkanolamine may containhydrocarbon substituents and particularly alkyl group or groups of fromone to about 50 and preferably of from one to 20 carbon atoms each orcycloalkyl groups and particularly cyclohexyl, or mixtures thereof.

The alkanolamine is reacted with the polycarboxylic acid, anhydride,diol or ester in any suitable manner. The reaction generally is effectedat a temperature above about 175 F. and preferably at a highertemperature, which usually will not exceed about 500 F., although higheror lower temperatures may be employed under certain conditions. Theexact temperature will depend upon whether a solvent is used and, whenemployed, on dialkanolamine particular solvent. For example, withbenzene as the solvent, the temperature will be of the order of 175 F.,with toluene the temperature will be of the order of about F., and withxylene Preferably order of 300- 320 F. Other preferred solvents includecumene, naphtha, decalin, etc. Any suitable amount of the solvent may beemployed but preferably should not comprise a large excess because thiswill tend to lower the reaction temperature and slow the reaction. Waterformed during the reaction may be removed in any suitable mannerincluding, for example, by operating under reduced pressure, by removingan azeotrope of water-solvent, by distilling the reaction product at anelevated temperature, etc. A higher temperature may be utilized in orderto remove the water as it is being formed. The time of reaction issufficient to effect the desired condensation and, in general, willrange from one-half to about 40 hours or more. When using a highertemperature within the range hereinbefore set forth, a shorter time ofreaction within the above range will be used, and vice versa. When usingthe dialkanolamine or the aminoalkyl alkanolamine, the time of reactionis sufficient to effect polymer formation and will be within the rangehereinbefore set forth and preferably will range from about 6 to about40 hours or more. preferably 1 to 2 mole proportions of the alkanolamineare reacted per 1 mole proportion of the acid, anhydride, diol or ester.

When the reaction product formed in the above manner is a polymer, itwill comprise polyesters and, when prepared from alkanolaminescontaining two or more amino groups, will include polyamides in additionto the polyesters. In another embodiment, the polymer may comprise amixed monoestermonoamide.

The reaction product generally is recovered as a viscous liquid. It maybe marketed and used as such or as a solution in a suitable solventincluding, for example, saturated paraffinic hydrocarbons includingpentane, hexane, heptane, octane, etc., aromatic hydrocarbons includingbenzene, toluene, xylene, cumene, etc., decalin, alcohols, ketones, etc.However, when the product is recovered in the absence of a solvent orwhen the product is not sufficiently soluble in the substrate, thedesired solubility may be obtained by dissolving the product in a mutualsolvent. Suitable solvents for this purpose comprise phenols andparticularly alkylphenols or polyalkylphenols in which the alkyl groupor groups contain from six to 20 carbon atoms. The phenol may be used ina concentration of from about 5 percent and preferably from about 25percent to about 500 percent by weight and, more particularly, fromabout 30 percent to about 200 percent by weight of the addition reactionproduct.

The addition reaction product of the present invention will have variedutility and is useful as an additive to organic substrates which undergooxidative deterioration. The additive functions as a lubricity orextreme pressure agent and also as a flame-proofing agent. In addition,the additive serves a detergent-dispersant, peroxide decomposer,corrosion inhibitor, rust inhibitor, etc. Organic substrates includegasoline, naphtha, kerosene, jet fuel, lubricating oil, diesel fuel,fuel oil, residual oil, drying oil, grease, wax, resin, plastic, rubber,etc.

The reaction product is used as an additive in lubricating oil. Thelubricating oil may be of natural or synthetic origin. The mineral oilsinclude those of petroleum origin and are referred to as motorlubricating oil, railroad type lubricating oil, marine oil, transformeroil, turbine oil, differential oil, diesel lubricating oil, gear oil,cylinder oil, specialty products oil, etc. Other oils include those ofanimal, marine or vegetable origin.

The lubricating oils generally have a viscosity within the range of from10 SUS at F. to 1,000 SUS at 210 F. (SAE viscosity numbers include therange from SAE 10 to SAE The petroleum oils are obtained fromparaffinic, naphthenic, asphaltic or mixed base crudes. When highlyparaffrnic lubricating oils are used, a solubilizing agent also is used.

Synthetic lubricating oils are of varied types including aliphaticesters, polyalkylene oxides, silicones, esters of phosphoric and silicicacids, highly fluorine-substituted hydrocarbons, etc. Of the aliphaticesters, di-(2-ethylhexyl) sebacate is being used on a comparativelylarge commercial scale. Other aliphatic esters include dialkyl azelates,dialkyl s'uberates, dialkyl pimelates, dialkyl adipates, dialkylglutarates, etc. Specific examples of these esters include dihexylazelate, di-(Z-ethylhexyl) azelate, di-3,5,5-trimethylhexyl glutarate,di-3,5,5-trimethylpentyl glutarate, di-(Z-ethylhexyl) pimelate,di-(2-ethylhexyl) adipate, triamyl tricarballylate, pentaerythritoltetracaproate, dipropylene glycol dipelargonate,l,5-pentane-diol-di-(2ethylhexanonate), etc. The polyalkylene oxidesinclude polyisopropylene oxide, polyisopropylene oxide diether,polyisopropylene oxide diester, etc. The silicones include methylsilicone, methylphenyl silicone, etc., and the silicates include, forexample, tetraisooctyl silicate, etc. The highly fluorinatedhydrocarbons include fluorinated oil, perfluorohydrocarbons, etc.

Additional synthetic lubricating oils include (1) neopentyl glycolesters in which the ester group contains from three to 12 carbon atomsor more, and particularly neopentyl glycol propionates, neopentyl glycolbutyrates, neopentyl glycol caproates, neopentyl glycol caprylates,neopentyl glycol pelargonates, etc., (2) trimethylol alltane esters suchas the esters of trimethylol ethane, trimethylol propane, trimethylolbutane, trimethylol pentane, trimethylol hexane, trimethylol heptane,trimethylol octane, trimethylol decane, trimethylol undecane,trimethylol dodecane, etc., and particularly triesters in which theester portions each contain from three to 12 carbon atoms and may beselected from those hereinbefore specifically set forth in connectionwith the discussion of the neopentyl glycol esters, (3) complex esterscomposed of dibasic acids and glycols, especially neopentyl, neohexyl,etc., glycols further reacted or capped with monobasic acids or alcoholsto give lubricants of viscosities at 210 F. of from four to 12centistokes or higher, and (4) tricresylphosphate, trioctylphosphate,trinonylphosphate, tridecylphosphate, as well as mixed aryl and alkylphosphates, etc.

The present invention also is used in greases made by compositing one ormore thickening agents with an oil of natural or synthetic origin. Metalbase synthetic greases are further classified as lithium grease, sodiumgrease, calcium grease, barium grease, strontium grease, aluminumgrease, etc. These greases are solid or semisolid gels and, in general,are prepared by the addition to the lubricating oil of hydrocarbonsoluble metal soaps or salts of higher fatty acids as, for example,lithium stearate, calcium stearate, aluminum naphthenate, etc. Thegrease may contain one or more thickening agents such as silica, carbonblack, talc, organic modified Bentonite, etc., polyacrylates, amides,polyamides, aryl ureas, methyl N-n-octadcyl terephthalomate, etc.Another type of grease is prepared from oxidized petroleum wax, to whichthe saponifiable base is combined with the proper amount of the desiredsaponifying agent, and the resultant mixture is processed to produce agrease. Other types of greases in which the features of the presentinvention are usable include petroleum greases, whale grease, woolgrease, etc., and those made from inedible fats, tallow, butcher'swaste, etc.

Oils of lubricating viscosity also are used as transmission fluids,hydraulic fluids, industrial fluids, etc., and the novel features of thepresent invention are used to further improve the properties of theseoils. During such use the lubricity properties of the oil are important.Any suitable lubricating oil which is used for this purpose is improvedby incorporating the additive of the present invention.

Oils of lubricating viscosity also are used as cutting oils, rollingoils, soluble oils, drawing compounds, etc. in this application, the oilis used as such or as an emulsion with water. Here again, it is desiredthat the oil serves to lubricate the metal parts of saws, knives,blades, rollers, etc., in addition to dissipating the heat created bythe contact of the moving metal parts.

Oils of lubricating viscosity also are used as slushing oils, Theslushing oils are employed to protect finished or unfinished metalarticles during storage or transportation from one area to another. Themetal articles may be of any shape or form including steel sheets,plates, panels, coils, bars, etc., which may comprise machine parts,engines, drums, piston rings, light arms, etc., as well as farmmachinery, marine equipment, parts for military or other vehicles,household equipment, factory equipment, etc. A coating which may bevisible to the eye, or not, as desired, covers the metal part andprotects it from corrosion, etc.

In another embodiment the addition reaction products of the presentinvention possess insecticidal properties with good inner-therapeuticaction. They may be employed against many types of mites and insectssuch as, for example, Corausius larvae, Cotoneaster aphid, apple aphid,black bean aphid, aster aphid, green peach aphid, chrysanthemum aphid,pea aphid, etc. The reaction products or mixture of these may be usedfor the control of various larvae, mites, eggs of mites and such insectsas flour beetle, mexican bean beetle, black carpet beetle, milkweed bug,german cockroaches, southern army worms,

mealy bug, sow bug, citrus red spider, greenhouse red spider, variousmosquitoes, yellow fever mosquito, malarial mosquito, houseflies, etc.

As hereinbefore set forth, the addition reaction products of the presentinvention also possess flame-proofing or flame retardant properties and,therefore, are useful in plastics, resins, coatings, paints, dryingoils, etc., as well as in fibrous materials. For example, in textiles,the reaction product imparts flame retardant properties to the fabric.

The plastics and resins include polyolefins such as polyethylene,polypropylene, polybutylene, etc., mixed polymers prepared from two ormore of ethylene, propylene and butylene, mixed polymers of one or moreeach of monoolefins and diolefins, polydiolefins includingpolybutadiene, polystyrene, polyvinylchloride, polycarbonate, ABS(acrylonitrile-butadiene-styrene polymer), polyphenyl ethers, polyphenylethers modified with styrene, polyesters, polyurethanes, epoxy resins,etc.

The concentration of the reaction product to be employed as an additivewill depend upon the particular substrate in which it is to be used. Ingeneral, the additive is used in a concentration of from about 0.001 toabout 25 percent by weight of the substrate and more specifically withinthe range of from about 0.01 to about 5 percent by weight of thesubstrate. When used in conventional lubricating oil, the additivegenerally may be employed in a concentration of from about 0.01 to about2 percent by weight of the oil. When used in lubricating oil for moresevere operations, such as hypoid gear oil, the additive is used in aconcentration of from about 1 to about 20 percent or more by weight ofthe oil. In general, substantially the same range of additiveconcentration is employed when the oil is used as transmission fluid,hydraulic fluid, industrial fluid, etc. When the oil is used in theformulation of a grease, the additive is used in a concentration of fromabout 0.5 to 5 percent by weight of the oil. When used in cutting oil,rolling oil, drawing compound, etc., the additive may be used in aconcentration of from about 0.l to about l0 percent by weight of theoil. When used in slushing oil, the additive may be used in aconcentration of from about 0.1 to about 15 percent by weight or more ofthe oil.

it is understood that the additive of the present invention may be usedalong with other additives incorporated in the or ganic substrate. Theother additives will depend upon the particular organic substrate. Forexample, in lubricating oil, the additional additives may comprise oneor more of viscosity index improver, pour point depressant, antifoamadditive, detergent, corrosion inhibitor, antioxidant, etc. Preferredantioxidants are of the phenolic type and include tertiarybutylcatechol,2,6-ditertiarybutyl-4-methylphenol, 2,4-dimethyl-6- tertiarybutylphenol,etc., 2-tertiarybutyl-4-methoxyphenol, 2- tertiary-4-ethoxyphenol,3,3',5,5-tetratertiarybutyl'diphenylmethane, etc.

When desired, an emulsifying agent may be employed in formulationscontaining the additive of the present invention. Any suitableemulsifying agent can be used, including alkali metal sulfonates ofpetroleum solfonic acids, mahogany sulfonates, naphthenic acids, fattyacids, etc., fatty alcohol sulfonates, pentaerythritol oleates,laurates, etc. The amount of water used in the emulsified oils willdepend upon the particular use of the emulsion and may range from 0.25to 50 percent or even up to 98 percent by weight of the composition.

The additive of the present invention is incorporated in the substratein any suitable manner and preferably the mixture is suitably agitatedor otherwise mixed in order to obtain intimate admixing of the additiveand of the substrate. When the substrate comprises a mixture of two ormore components, the additive of the present invention may be commingledwith one of the components prior to mixing with the remaining componentor components of the substrate.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

.2 EXAMPLE 1 The reaction product of this example is a polymericreaction product of A" anhydride (5,6,7,8,9,9-hexachloro- 1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride) withN-tallow-diethanolamine (Ethomeen T/12). The polymeric reaction productwas prepared by refluxing 106.25 g. (0.25 mole) of the A" anhydride and92 g. (0.25 mole) of the N-tallow-diethanolamine in the presence of 200g. of xylene. Refluxing was continued for about 7 hours at a maximumtemperature of about 300 F., during which time a total of 4.5 cc. ofwater was collected. Following completion of the reaction, the xylenesolvent was removed by distilling under water pump vacuum at a maximumtemperature of about 330 F. The polymeric reaction product had a basicnitrogen equivalent of 1.31 meqJg. and a basic mole combining weight of764, the latter corresponding to the theoretical mole combining weightof 775. 26.3 percent Chlorine was found to be contained in the additive.Average osmometric molecular weight was 2,065 at 0.43 percent asdetermined in chloroform.

EXAMPLE 11 The reaction product of this example was prepared by reactingA" anhydride with N,N'-dioctyl-N-hydroxyethylaminoethyl-ethanolamine.The alkanolamine was prepared by the oxyethylenation ofN,N'-dioctyl-ethylenediamine. The polymeric reaction product wasprepared by refluxing 47.4 g. (0.125 basic equivalent) of the aminoethylethanolamine and 53 g. (0.125 acidic equivalent) of the .A" anhydride inthe presence of 200 g. of xylene. The refluxing was continued for about9 hours and a total of 2 cc. of water was collected. The xylene solventwas removed by distilling under water pump vacuum at a temperature ofabout 400 F. The polymeric reaction product had a basic nitrogenequivalent of 2.33 meqJg. and a basic mole combining weight of 429.

EXAMPLE Ill The reaction product of this example was prepared byreacting A" anhydride with N-diethyl-ethanolamine. The reaction wasefi'ected by refluxing 106.25 g. (0.25 mole) of A" anhydride and 59 g.(0.5 mole) of N-diethylethanolamine in the presence of 100 g. oftoluene. 4.5 cc. of water was collected. The reaction product wasrecovered as a greasy product having a basic nitrogen equivalent of 2.97meq./g. which corresponds to the theoretical basic nitrogen equivalentof 3.19 meq./g.

EXAMPLE IV The reaction product of this example is a polymeric reactionproduct prepared by reacting Chlorendic" anhydride withN-tallow-diethanolamine (Ethomeen T/ 12). The polymeric reaction productwas prepared by refluxing 185.4 g. (0.5 mole) of Chlorendic" anhydrideand 184 g. (0.5 mole) of N-tallow-diethanolamine. The refluxing wascontinued for 6 hours at a temperature of about 310 F. and a total of 9cc. of water was collected. The xylene solvent was removed by heatingthe product at 275 F. under water pump vacuum. The polymeric reactionproduct has a basic nitrogen equivalent of 1.10 meq./g.

EXAMPLE V The reaction product of this example was prepared by reactingthe diol corresponding to Chlorendic" acid, N-tallow-diethanolamine(Ethomeen T/ 12) and dodecenyl succinic anhydride. The diol is preparedby reacting hexachlorocyclopentadiene with 1,4-butenediol. The polymericreaction product is prepared by refluxing 45.13 g. (0.125 mole) of theChlorendic diol, 48 g. (0.125 mole) of N-tallowdiethanolamine and 70.5g. (0.25 mole) of dodecenyl succinic anhydride. The refluxing iseffected at a temperature of about 340 F. for about 8 hours and a totalof 4.5 cc. of water is collected. The xylene solvent is removed bydistilling at a temperature up to about 350 F. under water pump vacuum.The product is recovered as a very heavy amber oil containing 16.3percent chlorine corresponding to the theoretical content of 16.7percent.

EXAMPLE V1 The reaction product of this example was prepared by reactingA anhydride, N-tallow-diethanolamine and dodecenyl succinic anhydride.The polymeric reaction product was prepared by refluxing 53 g. (0.125moles) of A" anhydride, 92 g. (0.25 mole) of N-tallow-diethanolamine and32.78 g. (0.125 moles) of dodecenyl succinic anhydride. A total of 4.5cc. of water was collected. Following completion of the reaction, thereaction mixture was distilled under water pump vacuum to remove thexylene solvent. A 50 percent lubricating oil solution of the product wasmade. The reaction product solution had a basic nitrogen equivalent of0.74

meq./g.

EXAMPLE Vll The reaction product of this example is prepared by reactingan ethyl ester of B acid (5,6,7,8,9,9-hexachloro- 1,2,3,4,4a,5,8,8a-octahydro-1,4,5,8-dimethano-2,3-naphthalenedicarboxylic acid) with N-decyl-aminopropylpropanolamine. Theester of 8" acid and ethyl alcohol is prepared by refluxing equal moleproportions of the acid and alcohol under conditions to liberate water,the water being removed simultaneously during the reaction. Theresulting ester and N-decyl-aminopropyl-propanolamine are refluxed inthe presence of xylene solvent to liberate water and to form thepolymeric reaction product.

EXAMPLE VIII The reaction product of this example is prepared byreacting A acid and N-soya-diethanolamine. The reaction is effected byrefluxing equal mole proportions of the A" acid andN-soya-diethanolamine and removing the water formed during the reaction.The resultant polymeric reaction product is recovered as an amber oil.

EXAMPLE [X In one embodiment the reaction products of the presentinvention are used as additives in lubricating oil. One method ofevaluating lubricating oils is by the Falex machine. This procedure isdescribed in detail in a book entitled Lubricant Testing" authored by E.G. Ellis and published by Scientific Publications (Great Britain)Limited, 1953, pages -154. Briefly, the Falex machine consists of arotating pin which runs between two V shape bearings which are springloaded against the pin and provided with means for varying the load. Theoil to be tested is poured into a metal trough in which the pin andbearings are partly submerged. The machine was operated for 5 minuteseach at 250 and 500 pound loads and then 45 minutes at 750 pound load.The data collected includes the temperature of the oil at each of theloads, as well as the wear which is determined by a ratchet wheelarrangement in which the teeth are advanced in order to maintain thedesired load. Each tooth is equivalent to approximately 0.000022 inches.Preferred additives are those which impart low temperature, low torqueand low wear to the oil.

In another series of tests the machine was operated for 5 minutes ateach load from 250 pounds to seizure at 250 pound increments. Themaximum load and the time in minutes at this load to seizure arereported, as well as the temperature of the oil. ln this case the highertemperature is preferred because it means that the oil is operatingsatisfactorily at a higher temperature.

The lubricating oil used in this example is dioctyl sebacate syntheticlubricating oil marketed under the trade name of Plexol 201."

exol" not containing an additive and thus is the blank or mud run.

Run No. 2 is a run made using another sample of Plexol ASTM-CFR (Erdco)Coker Test D-l660 using 6 p.p.h. fuel flow. Commercial diesel fuel hasbeen used as the testing medium. The preheater temperature has been setat 400 F. The filter temperature has been set at 932 F. 0.001 percentwhich had been added 2 percent by weight of the reaction by weight ofthe additive has been added to the fuel. The time roduct prepared asdescribed in example I. in minutes to reach the correspondingdifferential (AP) of Run No. 3 is a run made using another sample ofPlexol" mercury pressure is reported. While the control sample of thewhich had been added 2 percent by weight of the reaction fuel containingno additive reached the differential pressure of roduct prepared asdescribed in example ll. 25 inches of mercury in 87 minutes, 0.001percent by weight Run 4 is a made using another Sample of of theadditives of the present invention reduced the filter WhlCh had beenadded 2 percent by weight of the reaction l gi n iderably, a shown bythe data in the following roduct prepared as described in example ill gbl 7 TABLE I Tempearture, F. Torque, lbs. Wear, teeth Seizure conditions7 Temti tun No. 250 500 750 250 500 750 250 500 750 Load Time 231 490-83-4 9-10 18-8 0 0 S 750 2 490 215 463 4-5 10-14 21-40 0 0 166 1,750 1.172 240 513 4-6 11-13 22-37 0 0 204 1,500 2.0 715 218 513 4-6 10-12 25-350 0 205 1,500 2.0 725 N9 -fsi ll! J. .1...

From the above data, it will be seen that the dioctyl 25 TABLElilebacate without additive (Run No. 1) underwent seizure at a Time APinches pad of 750 pounds. The samples containing the additives ofMinutes r Hq he present invention did not undergo seizure until loads of50 750 pounds Run No. l Blank fuel 87 25 r No additive Run No. 0.001%product of 300 1.: EXAMPLE X example I Another series of evaluationswere made in the same Run 2 ggxgf 'w 300 L0 nanner as described inexample 1X, except that the lubricat- Run 3 om orwive 300 ng oil was amineral oil marketed commercially by A. H. inuwdifinlof :arnes Companyas Carnes 340 White Oil." Typical specifiample :ations of this oilinclude the following:

Distillation range, F. 740-975 fi gzf g 2:: 40 The above data illustratethat the reaction products of the 2 ,6. 522 present inventioneffectively reduce filter plugging of the fuel. Flash point, coc, F. 440Pour Point, F. -20 EXAMPLE X" Refractive index at 68 F. IABOS I Sayboltcolor +30 An insecticidal composltlon is prepared by dissolving l g. of

Run No. 5 in the following table is a run using the white oil notcontaining an additive and thus is the blank or control run.

Run No. 6 is a run using another sample of the white oil to which hadbeen added 2 percent by weight of the reaction product of example i.

Run No. 7 is a run using another sample of the white oil to which hadbeen added 2 percent by weight of the reaction product of example ll.

Run No. 8 is a run using another sample of the white oil to which hadbeen added 2 percent by weight of the reaction product of example Ill.

Here again, it will be noted that the use of the additives considerablyincreased the load at which seizure occurred as compared to the oilwithout additive (Run No. 5).

EXAMPLE Xi High temperature detergency and dispersant properties of thereaction products of the invention have been tested in the reactionproduct of example ill in 2 cc. of benzene and emulsifying the resultantsolution with cc. of water using Triton X-lOO as the emulsifying agent.The resulting emulsion is sprayed into a cage containing houseflies andresults in substantial knockdown.

EXAMPLE Xlll The reaction product of this example is prepared byreacting A" acid with N-octyl-ethanolamine. The reaction is effected byheating and mixing two mole proportions of the allranolamine with onemole proportion of the A" acid at a temperature of about 400 F. for aperiod of about l5 minutes, while nitrogen is being passed through thereaction mixture to remove the water of reaction, following which thereaction mixture is further heated and mixed at about 400 F. under avacuum of about 15 mm. Hg. for about an additional 15 minutes in orderto complete the reaction. The product is recovered as a viscous liquid.

I claim as my invention:

TAB LE II Temperature, F. Torque, lbs. Wear, teeth Seizure conditionsTemp., Ruu No. 250 500 750 250 500 750 250 500 750 Load Tune F.

5 172 350S 6-6 30-8 D S 425 0 1 275 267 535 5-6 13-15 22-45 0 2 60 1,750 4. 8 800 303 683 45 15-18 25-48 0 0 116 1, 500 2. 0 675 365 575 5-617-22 21-38 0 0 281 1, 250 1 0 650 Norm-S =seizure. A

l. The reaction product formed by the condensation at a wherein X ishalogen, hydrogen, or alkyl of from one to 10 carbon atoms, at least twoof the Xs being halogen, Y is halogen, hydrogen or alkyl of from one tocarbon atoms, m is an integer of from one to four, n ranges from zero tofour and p ranges from zero to four.

2. The reaction product of claim 1 wherein said compound isS,6,7,8,9,9-hexachloro-l,2,3,4,4a,5,8,8a-octanhydro-5,8-methano-2,3-naphthalencdicarboxylic acid.

3. The reaction product of claim 1 wherein said compound is 5,6,7,8,9,9-hexachlorol ,2,3 ,4a,5 ,8,8a-octahydro-5 ,8-methano-2,3-naphthalenedicarboxylic anhydride.

4. The reaction product of claim 1 wherein said compound is5,6,7,8,9,9-hexachloro-l ,2,3,4,4a,5,8,8a-octahydrol,4,5,8-dimethano2,3-naphthalenedicarboxylic acid.

5. The reaction product of claim 1 wherein said compound is 5,6,7,8,9,9-hexachlorol ,2,3,4,4a,5,8,8a-octahydrol,4,5,8-dimethano-2,B-naphthalenedicarboxylic anhydride.

6. The reaction product of claim 1 wherein said compound isl,4,5,6,7,7-hexachlorodicyclo-(2.2.l )-5-heptene-2,3-dicarboxylic acid.

7. The reaction product of claim 1 wherein said alkanolamine is amonoalkanolamine containing from two to about 20 carbon atoms.

8. The reaction product of claim 1 wherein said alkanolamine isN-alkyl-dialkanolamine in which said alkyl group contains from one to 20carbon atoms.

9. The reaction product of claim 8 wherein said alkanolamine isN-alkyl-diethanolamine in which said alkyl group contains from one to 20carbon atoms.

10. The reaction product of claim 9 wherein said alkanolamine isN-tallow-diethanolamine.

11. The reaction product of claim 1 wherein said alkanolamine isN-dialkyl-alkanolamine in which said alkyl groups contain from one to 20carbon atoms each.

12. The reaction product of claim 11 wherein said alkanolamine isN-diethyl-ethanolamine.

13. The reaction product of claim 1 wherein said alkanolamine is anaminoalkyl alkanolamine.

14. The reaction product of claim 13 wherein said alkanolamine is anaminoethyl ethanolamine.

15. The reaction product of claim 13 wherein said alkanolamine isN,N-dialkyl-aminoethyl-ethanolamine in which said alkyl groups containfrom one to 20 carbon atoms each.

16. The reaction product of claim 13 wherein said alkanolamine isN,N-dioctyl-N-hydroXyethyl-aminoethyl ethanolamine.

17. The reaction product of claim 1 being a polyester result-

2. The reaction product of claim 1 wherein said compound is 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic acid.
 3. The reaction product of claim 1wherein said compound is 5,6,7,8,9,9-hexachloro-1,2,3,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride.
 4. The reaction product of claim 1wherein said compound is 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-1,4,5,8-dimethano2,3-naphthalenedicarboxylic acid.
 5. The reaction product of claim 1wherein said compound is 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-1,4,5,8-dimethano-2,3-naphthalenedicarboxylic anhydride.
 6. The reaction product of claim 1wherein said compound is 1,4,5,6,7,7-hexachlorodicyclo-(2.2.1)-5-heptene-2,3-dicarboxylic acid. 7.The reaction product of claim 1 wherein said alkanolamine is amonoalkanolamine containing from two to about 20 carbon atoms.
 8. Thereaction product of claim 1 wherein said alkanolamine isN-alkyl-dialkanolamine in which said alkyl group contains from one to 20carbon atoms.
 9. The reaction product of claim 8 wherein saidalkanolamine is N-alkyl-diethanolamine in which said alkyl groupcontains from one to 20 carbon atoms.
 10. The reaction product of claim9 wherein said alkanolamine is N-tallow-diethanolamine.
 11. The reactionproduct of claim 1 wherein said alkanolamine is N-dialkyl-alkanolaminein which said alkyl groups contain from one to 20 carbon atoms each. 12.The reaction product of claim 11 wherein said alkanolamine isN-diethyl-ethanolamine.
 13. The reaction product of claim 1 wherEin saidalkanolamine is an aminoalkyl alkanolamine.
 14. The reaction product ofclaim 13 wherein said alkanolamine is an aminoethyl ethanolamine. 15.The reaction product of claim 13 wherein said alkanolamine isN,N''-dialkyl-aminoethyl-ethanolamine in which said alkyl groups containfrom one to 20 carbon atoms each.
 16. The reaction product of claim 13wherein said alkanolamine is N,N''-dioctyl-N-hydroxyethyl-aminoethylethanolamine.
 17. The reaction product of claim 1 being a polyesterresulting from the condensation reaction of one mole proportion of anethyl ester of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-1,4,5,8,-dimethano-2,3-naphthalenedicarboxylic acid with from 1 to 2 moleproportions of N-decyl-aminopropyl-propanolamine at a temperature offrom about 175* F. to about 500* F. and for a time of from about 1/2 toabout 40 hours or more.